KR102145787B1 - Polarizing film with pressure-sensitive adhesive layer for transparent conductive membrane, laminate and image display device - Google Patents

Abstract

An object of the present invention is to provide a polarizing film provided with a pressure-sensitive adhesive layer for a transparent conductive film in which deterioration of the transparent conductive film is suppressed even when laminated on a transparent conductive film. Another object of the present invention is to provide a laminate in which the polarizing film provided with the pressure-sensitive adhesive layer for transparent conductive films and a substrate having a transparent conductive film are bonded, and an image display device using the laminate.
It is a polarizing film provided with an adhesive layer in which an adhesive layer is laminated on at least one side of an iodine-based polarizing film, and the iodine-based polarizing film contains 1 to 14% by weight of iodine and/or iodine ions, and has a thickness of 2 to 40 It is an iodine-based polarizing film having a transparent protective film having a moisture permeability of 1000 g/(m ² ·24h) or less on at least one side of an iodine-based polarizer of µm at 60°C and 90% RH, and the pressure-sensitive adhesive layer at 60°C and 90% RH It is a polarizing film provided with a pressure-sensitive adhesive layer for a transparent conductive film, characterized in that the saturated moisture content in is 3.5% by weight or less.

Description

Polarizing film, laminate, and image display device equipped with an adhesive layer for a transparent conductive film {POLARIZING FILM WITH PRESSURE-SENSITIVE ADHESIVE LAYER FOR TRANSPARENT CONDUCTIVE MEMBRANE, LAMINATE AND IMAGE DISPLAY DEVICE}

The present invention relates to a polarizing film provided with an adhesive layer for a transparent conductive film. In addition, the present invention relates to a laminate in which the polarizing film provided with the pressure-sensitive adhesive layer for a transparent conductive film and a member having a transparent conductive film are bonded together, and to an image display device using the laminate.

In recent years, a transparent conductive film such as an indium tin oxide (ITO) thin film has been widely used in various applications. For example, the transparent conductive film is formed on a side opposite to the side in contact with the liquid crystal layer of a transparent substrate constituting a liquid crystal cell of a liquid crystal display device using a liquid crystal cell such as an in-plane switching (IPS) method, and serves as an antistatic layer. It is known. In addition, the transparent conductive film in which the transparent conductive film is formed on a transparent resin film is used for an electrode substrate of a touch panel, and for example, a liquid crystal display device or an image display device used in a mobile phone or a portable music player, and the touch panel are combined. The input devices used by this method have been widely spread.

In a liquid crystal display device and an image display device using this transparent conductive film, in recent years, there is a strong demand for reduction in weight and thickness, and reduction in thickness and weight are also desired for polarizing films used in the liquid crystal display device, etc. Manufacturing methods are being studied in various ways.

As a method of manufacturing a thin polarizing film, for example, a thin polyvinyl alcohol (PVA) polymer layer formed on a resin substrate having a certain thickness is uniaxially stretched in an integrated state with a resin substrate, thereby forming a thin polarizing film on a resin substrate. A method of forming a film on a film (for example, refer to Patent Document 1) or a laminated film in which a resin layer made of a PVA resin is formed on one side of a base film is uniaxially stretched at the free end at a specific draw ratio to obtain a stretched film. , A method of forming a thin polarizer by dyeing the stretched film with a dichroic dye is known (see, for example, Patent Document 2).

Patent No. 491205 Specification Patent No. 5048120 Specification

When the transparent conductive film is used as an antistatic layer, a polarizing film provided with an adhesive layer is laminated on a liquid crystal cell having the antistatic layer, and an antistatic layer made of a transparent conductive film and a polarizing film are bonded through the adhesive layer. In addition, when a transparent conductive film is used as an electrode for a touch panel, the transparent conductive film for electrodes and a polarizing film provided with a pressure-sensitive adhesive layer may be bonded to each other.

The thin polarizing films obtained in Patent Documents 1 and 2 are all polarizing films of single-side protection in which one side of a polarizer is protected with a transparent protective film, and when the polarizing film is bonded to a liquid crystal cell with a transparent conductive film or the like, a polarizer and a transparent The conductive film is bonded through the adhesive. When a transparent conductive film is bonded to the polarizer surface of a single-sided iodine polarizer through an adhesive layer, a trace amount of iodine from the iodine polarizer seeps into the adhesive layer, which reaches the transparent conductive film and deteriorates the transparent conductive film (corrosion). I could see what was being told. When the transparent conductive film deteriorates, for example, in the case where the transparent conductive film is used as an antistatic layer application, static electricity unevenness is generated in the liquid crystal panel and the antistatic performance is deteriorated. In addition, in the case of using the transparent conductive film as an electrode for a touch panel, the electrical resistance value increases due to deterioration of the electrode, resulting in malfunctions such as poor detection, or various problems such as a decrease in sensitivity of the touch panel. It was.

As a method of thinning a polarizing film, in addition to a method of thinning the polarizer itself as described in Patent Documents 1 and 2, a method of laminating a transparent protective film only on one side of the polarizer, there was also a method of thinning the thickness of the transparent protective film. . Even if it is a double-sided protective polarizing film having a transparent protective film on both sides of a polarizer, in the case of using the thin-filmed transparent protective film as a transparent protective film, iodine seeps into the pressure-sensitive adhesive from an iodine-based polarizer, causing a phenomenon in which the transparent conductive film is deteriorated. There was. In particular, in the thin transparent protective film having a high moisture permeability, it was found that the phenomenon is likely to occur.

Accordingly, an object of the present invention is to provide a polarizing film provided with a pressure-sensitive adhesive layer for a transparent conductive film, in which deterioration of the transparent conductive film is suppressed even when laminated on a transparent conductive film. Another object of the present invention is to provide a laminate in which the polarizing film provided with the pressure-sensitive adhesive layer for transparent conductive films and a member having a transparent conductive film are bonded, and an image display device using the laminate.

The inventors of the present invention found out that the above object can be achieved by controlling the moisture content of the pressure-sensitive adhesive layer and the moisture permeability of the transparent protective film as a result of earnestly examining in order to solve the above problems, and came to complete the present invention.

That is, the present invention is a polarizing film provided with an adhesive layer in which an adhesive layer is laminated on at least one side of an iodine-based polarizing film,

The iodine-based polarizing film contains 1 to 14% by weight of iodine and/or iodine ions, and on at least one side of an iodine polarizer having a thickness of 2 to 40 μm, the moisture permeability at 60° C. and 90% RH is 1000 g/( m ² · 24 h) or less, which is an iodine polarizing film having a transparent protective film,

It relates to a polarizing film provided with a pressure-sensitive adhesive layer for a transparent conductive film, wherein the pressure-sensitive adhesive layer has a saturated moisture content of 3.5% by weight or less at 60°C and 90% R.H. Here, the ``iodine polarizer containing iodine and/or iodine ion'' refers to an iodine polarizer containing iodine, an iodine polarizer containing iodine ions, and an iodine polarizer containing both iodine and iodine ions. In the invention, all can be suitably used.

It is preferable that the value obtained by multiplying the polarizer thickness (µm) and the iodine content (wt%) of the iodine polarizer is 10 to 80 wt%·µm.

The iodine-based polarizing film is a one-sided protective polarizing film having a transparent protective film only on one side of the iodine-based polarizing film, and the surface of the one-sided protective polarizing film which does not have a transparent protective film and the pressure-sensitive adhesive layer may be in contact. .

It is preferable that the transparent conductive film is formed of indium tin oxide, and it is preferable that the indium tin oxide is amorphous indium tin oxide.

In addition, the present invention provides a transparent conductive member having a transparent conductive film and a polarizing film provided with a pressure-sensitive adhesive layer for a transparent conductive film, so that the pressure-sensitive adhesive layer of the polarizing film provided with the pressure-sensitive adhesive layer for a transparent conductive film and the transparent conductive film of the member are in contact with each other. It relates to a laminate characterized by bonding.

Further, the present invention relates to an image display device characterized by using the laminate. In the image display device, the transparent conductive member having the transparent conductive film may be a member including a transparent conductive film and a liquid crystal cell, or the transparent conductive member having the transparent conductive film is a transparent conductive film having a transparent conductive film, and the You may use a laminated body as a touch panel.

It was found that the deterioration of the transparent conductive film by iodine tends to proceed as the moisture content in the pressure-sensitive adhesive contacting the transparent conductive film increases. Therefore, the present invention is a case in which a transparent conductive film is laminated on the pressure-sensitive adhesive layer of a polarizing film provided with a pressure-sensitive adhesive layer for a transparent conductive film by controlling the moisture content of the pressure-sensitive adhesive layer itself or the moisture permeability of the protective film, which are factors related to the moisture content of the pressure-sensitive adhesive layer. Edo can suppress the deterioration of the transparent conductive film.

1. Polarizing film with adhesive layer for transparent conductive film

In the polarizing film provided with the pressure-sensitive adhesive layer for transparent conductive films of the present invention, the pressure-sensitive adhesive layer is laminated on at least one side of an iodine-based polarizing film,

The iodine-based polarizing film contains 1 to 14% by weight of iodine and/or iodine ions, and on at least one side of an iodine polarizer having a thickness of 2 to 40 μm, the moisture permeability at 60° C. and 90% RH is 1000 g/( m ² · 24 h) or less, which is an iodine polarizing film having a transparent protective film,

The pressure-sensitive adhesive layer is characterized in that the saturated moisture content at 60°C and 90% R.H. is 3.5% by weight or less.

(1) Iodine polarizing film

The iodine-based polarizing film used in the present invention contains 1 to 14% by weight of iodine and/or iodine ions, and on at least one side of an iodine polarizer having a thickness of 2 to 40 μm, moisture permeability at 60° C. and 90% RH It has a transparent protective film of 600 g/(m ² ·24h) or less. In the present invention, a single-sided protective polarizing film having a transparent protective film on one side of the iodine-based polarizer may be used, or a double-sided protective polarizing film having a transparent protective film on both sides of the iodine-based polarizer, but the present invention is used when a single-sided protective polarizing film is used. The effect of is remarkable. Moreover, even if it is a double-sided protective polarizing film, even when the thickness of the transparent protective film on the side in contact with the pressure-sensitive adhesive layer is thin (for example, 25 μm or less), the effect of the present invention is remarkable. In addition, when the polarizing film is a single-sided protective polarizing film, the pressure-sensitive adhesive layer may be provided directly on the surface of the polarizer on the side not having the transparent protective film.

In addition, the content of iodine and/or iodine ions in the iodine polarizer used in the present invention (hereinafter, sometimes referred to as iodine content) is 1 to 14% by weight, 2 to 12% by weight, or 4 It may be 11% by weight. When the iodine content is less than 1% by weight, since the amount of iodine transferred from the iodine-based polarizer to the transparent conductive film is small, deterioration of the transparent conductive film does not occur, but polarization characteristics as a polarizer are not sufficient. In addition, when the iodine content exceeds 14% by weight, the deterioration of the transparent conductive film is large, causing static unevenness or deterioration of the shielding performance. In addition, when the iodine polarizer is a thin polarizer described later, the iodine content is preferably 4 to 12% by weight, and more preferably 4 to 11% by weight.

The polarizing film provided with the pressure-sensitive adhesive layer for a transparent conductive film of the present invention is transparent when a transparent conductive film is laminated on the pressure-sensitive adhesive layer of the polarizing film provided with the transparent conductive film, even when the iodine content of the iodine-based polarizer is high. Deterioration of the conductive film due to iodine can be suppressed. As a result, when the said polarizing film is incorporated in a liquid crystal panel, it does not generate|occur|produce static electricity unevenness, and shielding performance can be exhibited effectively. Deterioration of the transparent conductive film occurs when iodine in the iodine polarizer passes through the pressure-sensitive adhesive to reach the transparent conductive film, but it was found that the deterioration due to the iodine tends to proceed as the moisture content in the pressure-sensitive adhesive layer increases. In the present invention, as described later, deterioration of the transparent conductive film due to iodine can be suppressed by suppressing the moisture content of the pressure-sensitive adhesive itself, which is a factor related to the moisture content of the pressure-sensitive adhesive layer, and the moisture permeability of the protective film.

The thickness of the iodine polarizer is 2 to 40 µm, preferably 2 to 25 µm, and more preferably 3 to 10 µm. If the thickness of the iodine polarizer is thicker than 40 µm, the amount of iodine contained in the iodine polarizer increases and deterioration of the transparent conductive film increases. Further, a thin iodine polarizer having a thickness of 10 µm or less is preferable because it has little thickness unevenness, excellent visibility, and has little dimensional change, so it is excellent in durability, and further, the thickness as a polarizing film can be reduced.

As the iodine polarizer, it is a polarizer containing 1 to 14% by weight of iodine and/or iodine ions, and any one having a thickness of 2 to 40 μm can be used. For example, a polyvinyl alcohol (PVA) film, A hydrophilic polymer film such as a partially formalized PVA-based film and an ethylene/vinyl acetate copolymer-based partially saponified film may be uniaxially stretched by adsorbing iodine. Among these, a polarizer made of a PVA-based film and iodine is suitable.

The polarizer obtained by uniaxially stretching a PVA-based film by dyeing it with iodine can be produced by, for example, dyeing by immersing PVA in an aqueous solution of iodine and stretching to 3 to 7 times the original length. If necessary, it may be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, or zinc chloride. Further, if necessary, before dyeing, the PVA-based film may be immersed in water and washed with water. By washing the PVA-based film with water, it is possible to wash the surface of the PVA-based film with an anti-blocking agent or contamination, and by swelling the PVA-based film, there is an effect of preventing unevenness such as staining of dyeing. Stretching may be performed after dyeing with iodine, stretching may be performed while dyeing, or may be dyed with iodine after stretching. It can be stretched even in an aqueous solution such as boric acid or potassium iodide or in a water bath.

In addition, as a thin iodine polarizer having a thickness of 10 μm or less, representatively, Japanese Patent Laid-Open No. 51-069644, Japanese Patent Laid-Open No. 2000-338329, International Publication No. 2010/10917 pamphlet, and International Publication No. A thin polarizing film described in the pamphlet of 2010/100917 or the specification of Patent No. 4751481 or Japanese Patent Laid-Open No. 2012-073563 may be exemplified. These thin polarizing films can be obtained by a manufacturing method including a step of stretching a PVA-based resin layer and a resin substrate for stretching in the state of a laminate and a step of dyeing. With this manufacturing method, even if the PVA-based resin layer is thin, it becomes possible to stretch without problems such as fracture due to stretching by being supported by the resin substrate for stretching.

As the thin polarizing film, among the manufacturing methods including the step of stretching and dyeing in the state of a laminate, since it can be stretched at a high magnification and thus the polarization performance can be improved, International Publication No. 2010/100917 Pamphlet, International Publication No. It is preferable that it is obtained by a manufacturing method including a step of stretching in an aqueous boric acid solution as described in the pamphlet of Unexamined Publication No. 2010/100917 or the specification of Patent No. 4751481 or Japanese Unexamined Patent Publication No. 2012-073563. In particular, the specification of Patent No. 4751481 or Japan It is preferable to obtain by a manufacturing method including a step of auxiliary air stretching before stretching in the aqueous boric acid solution described in Patent Publication No. 2012-073563.

In addition, the value obtained by multiplying the iodine concentration and the thickness of the iodine polarizer is preferably 10 to 80% by weight·µm, more preferably 15 to 70% by weight·µm, and 18 to 50% by weight·µm. More preferable. When this value is 10% by weight or less, the amount of iodine transferred from the iodine-based polarizer to the transparent conductive film is small, so deterioration of the transparent conductive film does not occur, but the polarization characteristics as a polarizer may not be sufficient. If it exceeds 80% by weight·µm, there is a tendency that the deterioration of the transparent conductive film increases.

Of the iodine-based polarizer on one side, or, a transparent protective film to be provided on both sides is, the 60 ℃, water vapor transmission rate of from 90% R · H · less than ^{1000g / (m 2 · 24h)} , 700g / (m 2 · 24h) It is preferably less than or equal to 500 g/(m ² ·24h) or less, more preferably less than or equal to 300 g/(m ² ·24h), and most preferably less than 150 g/(m ² ·24h). If the moisture permeability of the transparent protective film is greater than the above range, the moisture content in the pressure-sensitive adhesive increases due to the increased amount of moisture that penetrates through the transparent protective film, so when the pressure-sensitive adhesive optical film having the pressure-sensitive adhesive layer is bonded to the transparent conductive film , Deterioration of the transparent conductive film due to iodine is likely to occur. Further, when the polarizing film is incorporated in a liquid crystal panel having a transparent conductive film, static electricity unevenness occurs or the shielding performance deteriorates, which is not preferable. In addition, when the moisture permeability of the transparent protective film is low, the lower one is effective, and the lower limit is not particularly limited. The moisture permeability measurement method of the transparent protective film can be performed by the method described in Examples.

As a material for forming the transparent protective film provided on one side or both sides of the iodine polarizer, those excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, isotropic properties, and the like are preferable. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, polystyrene or acrylonitrile-styrene copolymer Styrene polymers, such as (AS resin), polycarbonate polymers, etc. are mentioned. In addition, polyethylene, polypropylene, polyolefin having a cyclo- or norbornene structure, polyolefin-based polymers such as ethylene-propylene copolymers, vinyl chloride-based polymers, amide-based polymers such as nylon or aromatic polyamide, imide-based polymers, alcohol Pone polymer, polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, Epoxy-based polymers, or blends of the polymers are also exemplified as examples of polymers forming the transparent protective film. The transparent protective film can also be formed as a resin cured layer of a thermosetting type, such as an acrylic type, a urethane type, an acrylic urethane type, an epoxy type, and a silicone type, and an ultraviolet curing type.

The thickness of the transparent protective film can be appropriately determined, but in general, it is preferably about 1 to 500 µm, more preferably about 1 to 300 µm, in terms of workability such as strength and handling, thin film properties, etc. , More preferably, it is about 5 to 200 µm, more preferably about 5 to 200 µm, and particularly preferably about 10 to 80 µm.

Since the moisture permeability of the transparent protective film greatly affects not only the material of the transparent protective film, but also the thickness, it is determined by the balance between the material and the thickness. The thinner the transparent protective film, the higher the moisture permeability, and the thicker the lower the moisture permeability. Further, the moisture permeability may be adjusted by coating a material having low moisture permeability on the surface of the transparent protective film. For example, a transparent protective film having a predetermined moisture permeability can be obtained by applying an acrylic coating material having a low moisture permeability. Further, in the case of coating a material having a low moisture permeability, the thickness is not particularly limited, but may be, for example, about 5 to 30 µm.

The iodine polarizer and the transparent protective film are usually in close contact with each other through a water-based adhesive or the like. Examples of the water-based adhesive include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latex-based, water-based polyurethane, and water-based polyesters. In addition to the above, examples of the adhesive between the polarizer and the transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive. The adhesive for electron beam-curable polarizing films exhibits suitable adhesion to the above-described various transparent protective films. Moreover, a metal compound filler can be made to contain in the adhesive agent used by this invention.

The surface of the transparent protective film on which the iodine polarizer is not adhered may be treated with a hard coating layer, antireflection treatment, anti-sticking, or treatment for the purpose of diffusion or anti-glare.

(2) adhesive layer

The pressure-sensitive adhesive layer used in the present invention may have a saturated moisture content of 3.5% by weight or less at 60°C and 90% R.H., and its composition is not particularly limited. The saturated moisture content of the pressure-sensitive adhesive layer is preferably 0 to 2% by weight, more preferably 0 to 1.5% by weight, still more preferably 0 to 1.0% by weight, and particularly preferably 0 to 0.5% by weight or less. When the saturated moisture content of the pressure-sensitive adhesive layer exceeds 3.5% by weight, the amount of moisture contained in the pressure-sensitive adhesive layer is large, and when the polarizing film having the pressure-sensitive adhesive layer is bonded to the transparent conductive film, deterioration of the transparent conductive film due to iodine occurs. easy.

It is preferable that the pressure-sensitive adhesive layer in the present invention is formed of a pressure-sensitive adhesive composition containing a base polymer and a crosslinking agent. The pressure-sensitive adhesive composition may be an acrylic, synthetic rubber, rubber, or silicone pressure-sensitive adhesive, but from the viewpoint of transparency and heat resistance, an acrylic pressure-sensitive adhesive having a (meth)acrylic polymer as a base polymer is preferable.

The (meth)acrylic polymer used as the base polymer of the acrylic pressure-sensitive adhesive is preferably obtained by polymerizing a monomer component containing a (meth)acrylic acid ester having an alkyl group having 2 to 14 carbon atoms, and a (meth)acrylic polymer having an alkyl group having 2 to 14 carbon atoms. ) It is more preferable that it is obtained by polymerizing a monomer component containing an acrylic acid ester as a main monomer. Here, the main monomer is preferably 60% by weight or more, and more preferably 70% by weight or more with respect to all the monomer components constituting the (meth)acrylic polymer. In addition, (meth)acrylic acid ester means acrylic acid ester and/or methacrylic acid ester, and has the same meaning as (meth) of this invention.

As the (meth)acrylic acid ester having an alkyl group having 2 to 14 carbon atoms, for example, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylic Rate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth) Acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, etc. These can be mentioned, and these can be used individually by 1 type or in mixture of 2 or more types. Among these, a (meth)acrylic acid ester having an alkyl group having 4 to 14 carbon atoms is more preferable because its hydrophobic property is stronger.

The monomer component may contain other polymerizable monomers other than the (meth)acrylic acid ester having an alkyl group having 2 to 14 carbon atoms. The other polymerizable monomers are not particularly limited as long as they have a polymerizable functional group relating to an unsaturated double bond such as a (meth)acryloyl group or a vinyl group, but examples thereof include a hydroxyl group-containing monomer and a carboxyl group-containing monomer. I can.

As the hydroxyl group-containing monomer, one having a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group, and having a hydroxyl group can be used without particular limitation. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate. )Acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth) ) Acrylate and the like, and these can be used alone or in combination of two or more. The hydroxyl group-containing monomer is preferable because it has an effect of increasing the adhesion to the transparent conductive film (in particular, ITO). Among these, a hydroxyl group-containing acrylic monomer having 4 or more carbon atoms in the side chain is preferable because the effect of increasing the adhesion to the transparent conductive film is high and the hydrophobic property is stronger.

The content of the hydroxyl group-containing monomer is preferably 10% by weight or less in the monomer component, more preferably 0 to 5% by weight, and still more preferably 0.1 to 2% by weight. In addition, in the present invention, in particular, the hydrophilicity of the pressure-sensitive adhesive composition can be adjusted by using the content of the hydroxyl group-containing acrylic monomer having 4 or more carbon atoms in the side chain within the above range, and as a result, the saturated moisture content of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition It is preferable because it can be adjusted.

As the carboxyl group-containing monomer, one having a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group, and having a carboxyl group can be used without particular limitation. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc., and these may be used alone or in combination. Can be used.

The content of the carboxyl group-containing monomer is preferably 5% by weight or less in the monomer component. When the carboxyl group-containing monomer exceeds 5% by weight of the monomer component, the hydrophilicity of the pressure-sensitive adhesive composition increases, and the moisture content of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition tends to increase, which is not preferable.

Other copolymerization monomers are not particularly limited as long as they have a polymerizable functional group related to an unsaturated double bond such as a (meth)acryloyl group or a vinyl group, and examples thereof include cyclohexyl (meth)acrylate, bornyl (meth)acrylate, (Meth)acrylic acid alicyclic hydrocarbon esters such as isobornyl (meth)acrylate; For example, (meth)acrylic acid aryl esters such as phenyl (meth)acrylate; Vinyl esters, such as vinyl acetate and vinyl propionate, for example; For example, styrene-based monomers such as styrene; For example, epoxy group-containing monomers such as glycidyl (meth)acrylate and methylglycidyl (meth)acrylate; Amide group-containing monomers such as acrylamide, diethylacrylamide, acryloylmorpholine (ACMO), and N-vinylpyrrolidone (NVP); For example, amino group-containing monomers such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate; For example, cyclic nitrogen-containing monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and methylvinylpyrrolidone; For example, alkoxy group-containing monomers such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; Cyano group-containing monomers such as acrylonitrile and methacrylonitrile; Functional monomers, such as 2-methacryloyloxyethyl isocyanate, for example; For example, olefinic monomers such as ethylene, propylene, isoprene, butadiene and isobutylene; For example, vinyl ether monomers such as vinyl ether; Halogen atom-containing monomers such as vinyl chloride; N-vinylcarboxylic acid amides, etc. are mentioned.

Further, examples of the copolymerizable monomer include maleimide-based monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide; For example, N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclo Itaconimide-based monomers such as hexyl itaconimide and N-lauryl itaconimide; For example, N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, N-(meth)acryloyl-8-oxyoctamethylene Succinimide-based monomers such as succinimide; For example, styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloyloxynaphthalenesulfonic acid And sulfonic acid group-containing monomers.

In addition, as copolymerizable monomers, for example, glycol-based acrylic ester monomers such as polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, and methoxypolypropylene glycol (meth)acrylate. ; In addition, for example, a heterocycle such as tetrahydrofurfuryl (meth)acrylate or fluorine (meth)acrylate, an acrylic acid ester monomer containing a halogen atom, and the like can be mentioned.

In addition, a polyfunctional monomer can be used as the copolymerizable monomer. Examples of the polyfunctional monomer include compounds having two or more unsaturated double bonds such as a (meth)acryloyl group and a vinyl group. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetraethylene glycol di (meth) (Mono or poly)alkyl such as (mono or poly)ethylene glycol di(meth)acrylate such as acrylate or (mono or poly)propylene glycol di(meth)acrylate such as propylene glycol di(meth)acrylate In addition to ene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropanetri(meth) Esterified products of (meth)acrylic acid and polyhydric alcohols such as acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; Polyfunctional vinyl compounds such as divinylbenzene; And compounds having a reactive unsaturated double bond such as allyl (meth)acrylate and vinyl (meth)acrylate. In addition, as a polyfunctional monomer, a polyester (meth)acrylate in which two or more unsaturated double bonds such as (meth)acryloyl group and vinyl group are added as the same functional group as the monomer component to the skeleton of polyester, epoxy, urethane, etc. , Epoxy (meth)acrylate, urethane (meth)acrylate, etc. may also be used.

The ratio of the copolymerization monomer other than the hydroxyl group-containing monomer and the carboxyl group-containing monomer is preferably 40% by weight or less, more preferably 0 to 30% by weight, and still more preferably 0 to 10% by weight in the monomer component. However, since the amide group-containing monomer and the amino group-containing monomer may improve the hydrophilicity of the pressure-sensitive adhesive composition, each of the monomer components is preferably 10% by weight or less, and more preferably 8% by weight or less.

The weight average molecular weight of the (meth)acrylic polymer used in the present invention is preferably in the range of 1.2 million to 3 million, more preferably 1.2 million to 2.7 million, and still more preferably 1.2 million to 2.5 million. When the weight average molecular weight was less than 1.2 million, there were cases where it was not preferable from the viewpoint of heat resistance. In addition, when the weight average molecular weight is less than 1.2 million, the low molecular weight component increases in the pressure-sensitive adhesive composition, and the low molecular weight component bleeds out from the pressure-sensitive adhesive layer to impair transparency. Further, the pressure-sensitive adhesive layer obtained using a (meth)acrylic polymer having a weight average molecular weight of less than 1.2 million may have poor solvent resistance and mechanical properties. Further, when the weight average molecular weight is greater than 3 million, a large amount of diluting solvent is required to adjust the viscosity for application and construction, which is not preferable from the viewpoint of cost. Moreover, since the weight average molecular weight is in the said range, it is preferable also from a viewpoint of corrosion resistance and durability. The weight average molecular weight is measured by GPC (gel permeation chromatography) and refers to a value calculated in terms of polystyrene.

For the production of such (meth)acrylic polymers, known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations can be appropriately selected, and although not particularly limited, in the present invention, the viewpoint of the moisture content of the pressure-sensitive adhesive layer It is preferable that it is solution polymerization. Further, the obtained (meth)acrylic polymer may be any of a random copolymer, a block copolymer, and a graft copolymer.

In solution polymerization, ethyl acetate, toluene, etc. are used as a polymerization solvent. As a specific example of solution polymerization, a polymerization initiator is added under a stream of an inert gas such as nitrogen, and the reaction is usually carried out at a reaction condition of about 50 to 70°C for about 5 to 30 hours.

The polymerization initiator, chain transfer agent, emulsifier, and the like used for radical polymerization are not particularly limited and may be appropriately selected and used. In addition, the weight average molecular weight of the (meth)acrylic polymer can be controlled depending on the amount of the polymerization initiator and the chain transfer agent used, and the reaction conditions, and the amount of the (meth)acrylic polymer is appropriately adjusted according to the types of these.

As a polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane)dihydrochloride, 2,2'-azobis[2-(5- Methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine) disulfate, 2,2'-azobis(N,N'-di Methylene isobutylamidine), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate (trade name: VA-057, manufactured by Wako Pure Chemical Industries, Ltd.), etc. Azo initiators, potassium persulfate, persulfates such as ammonium persulfate, di(2-ethylhexyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, di-sec-butyl Peroxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1, 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, di(4-methylbenzoyl)peroxide, dibenzoylperoxide, t-butylperoxyisobutyrate, 1,1-di(t- Redox initiators that combine peroxides and reducing agents such as hexylperoxy)cyclohexane, t-butylhydroperoxide, and hydrogen peroxide, a combination of persulfate and sodium hydrogen sulfite, and a combination of peroxide and sodium ascorbate. Etc. are mentioned, but it is not limited to these.

The polymerization initiator may be used alone or in combination of two or more, but the overall content is preferably about 0.005 to 1 part by weight based on 100 parts by weight of the monomer component forming the (meth)acrylic polymer. Do.

As a chain transfer agent, for example, lauryl mercaptan, glycidyl mercaptan, mercapto acetic acid, 2-mercaptan ethanol, thioglycolic acid, thioglycolic acid 2-ethylhexyl, 2,3-dimercapto-1-propanol, etc. Can be mentioned. The chain transfer agent may be used alone or in combination of two or more, but the total content is about 0.1 parts by weight or less based on 100 parts by weight of the total amount of the monomer component.

Various silane coupling agents can be added to the pressure-sensitive adhesive composition used in the present invention in order to improve adhesion under high temperature and high humidity conditions. As the silane coupling agent, one having any suitable functional group can be used. As a functional group, a vinyl group, an epoxy group, an amino group, a mercapto group, a (meth)acryloxy group, an acetoacetyl group, an isocyanate group, a styryl group, a polysulfide group, etc. are mentioned, for example. Specifically, vinyl group-containing silane coupling agents such as vinyl triethoxysilane, vinyl tripropoxysilane, vinyl triisopropoxysilane, and vinyl tributoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. Epoxy group-containing silane coupling agent; γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, γ-triethoxysilyl Amino group-containing silane coupling agents such as -N-(1,3-dimethylbutylidene)propylamine and N-phenyl-γ-aminopropyltrimethoxysilane; mercapto group-containing silane coupling agents such as γ-mercaptopropylmethyldimethoxysilane; styryl group-containing silane coupling agents such as p-styryl trimethoxysilane; (meth)acrylic group-containing silane coupling agents such as γ-acryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane; An isocyanate group-containing silane coupling agent such as 3-isocyanate propyl triethoxysilane; Polysulfide group-containing silane coupling agents, such as bis(triethoxysilylpropyl) tetrasulfide, etc. are mentioned.

The silane coupling agent may be used alone or in combination of two or more, but the overall content is preferably 1 part by weight or less, and 0.01 to 1 part by weight based on 100 parts by weight of the base polymer (solid content). More preferably, it is more preferably 0.02 to 0.8 parts by weight. When the blending amount of the silane coupling agent exceeds 1 part by weight, unreacted coupling agent components are generated, which is not preferable from the viewpoint of durability.

Further, when the silane coupling agent can be copolymerized with the monomer component by radical polymerization, the silane coupling agent can be used as the monomer component. The ratio is preferably 0.005 to 0.7 parts by weight based on 100 parts by weight of the base polymer (solid content).

Furthermore, it is preferable to add a crosslinking agent to the pressure-sensitive adhesive composition used in the present invention, since cohesive force related to the durability of the pressure-sensitive adhesive can be imparted.

As a crosslinking agent, a polyfunctional compound is used, and an organic type crosslinking agent and a polyfunctional metal chelate are mentioned. Examples of the organic crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, a carbodiimide crosslinking agent, an imine crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, and a peroxide crosslinking agent. The polyfunctional metal chelate is one in which a polyvalent metal atom is covalently bonded or coordinated with an organic compound. Examples of polyvalent metal atoms include A1, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, and Ti. have. An oxygen atom etc. are mentioned as an atom in the organic compound which is covalently bonded or coordinated, and an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, a ketone compound, etc. are mentioned as an organic compound. These crosslinking agents can be used alone or in combination of two or more. Among these, a peroxide-based crosslinking agent and an isocyanate-based crosslinking agent are preferable, and a combination of them is more preferable.

An isocyanate-based crosslinking agent refers to a compound having two or more isocyanate groups (including an isocyanate regenerated functional group temporarily protected by a blocking agent or a water-quantizing agent) in one molecule.

Examples of the isocyanate crosslinking agent include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.

More specifically, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, and alicyclic isocyanates such as isophorone diisocyanate, 2,4- Aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, and polymethylene polyphenyl isocyanate, trimethylolpropane/tolylene diisocyanate trimer adduct (trade name: Coronate L, Nippon Polyurethane Industrial Co., Ltd.), trimethylolpropane/hexamethylene diisocyanate trimer adduct (trade name: Coronate HL, Nippon Polyurethane Industrial Co., Ltd.), isocyanurate of hexamethylene diisocyanate (trade name : Isocyanate adducts such as coronate HX and Nippon Polyurethane Industries Co., Ltd., trimethylolpropane adducts of xylene diisocyanate (trade name: D110N, manufactured by Mitsui Chemicals Co., Ltd.), trimethylolpropane of hexamethylene diisocyanate Additives (trade name: D160N, manufactured by Mitsui Chemicals Co., Ltd.); Polyether polyisocyanates, polyester polyisocyanates, and adducts of these and various polyols, polyisocyanates polyfunctionalized by isocyanurate bonds, biuret bonds, allophanate bonds, and the like. Among these, the use of an aliphatic isocyanate is preferable because the reaction rate is fast.

As the peroxide-based crosslinking agent, various peroxides are used. As a peroxide, di(2-ethylhexyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, di-sec-butylperoxydicarbonate, t-butylperoxyneode Decanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxyisobutyrate , 1,1,3,3-tetramethylbutylperoxy2-ethylhexanoate, di(4-methylbenzoyl)peroxide, dibenzoylperoxide, t-butylperoxyisobutyrate, and the like. Among these, di(4-t-butylcyclohexyl)peroxydicarbonate, dilauroyl peroxide, and dibenzoyl peroxide, which are particularly excellent in crosslinking reaction efficiency, are preferably used.

The blending ratio of the crosslinking agent in the pressure-sensitive adhesive composition is not particularly limited, but is usually blended in a ratio of about 10 parts by weight or less of the crosslinking agent (solid content) to 100 parts by weight of the base polymer (solid content). The blending ratio of the crosslinking agent is preferably 0.01 to 10 parts by weight, more preferably about 0.01 to 5 parts by weight. In particular, in the case of using a peroxide-based crosslinking agent, about 0.05 to 1 part by weight is preferable, and more preferably 0.06 to 0.5 parts by weight based on 100 parts by weight of the base polymer (solid content).

Furthermore, in the pressure-sensitive adhesive composition used in the present invention, if necessary, a viscosity modifier, a peel modifier, a tackifier, a plasticizer, a softener, a glass fiber, a glass beads, a filler, a pigment, a colorant ( Pigments, dyes, etc.), pH adjusters (acids or bases), antioxidants, ultraviolet absorbers, and the like, and various additives may be suitably used within a range not departing from the object of the present invention.

(3) Polarizing film with adhesive layer for transparent conductive film

The polarizing film provided with the adhesive layer for transparent conductive films of this invention is obtained by forming the adhesive layer on at least one surface of the said iodine-type polarizing film.

Although the method of forming the pressure-sensitive adhesive layer is not particularly limited, the pressure-sensitive adhesive composition is applied on various substrates, dried with a dryer such as a heat oven, and evaporated to evaporate a solvent to form a pressure-sensitive adhesive layer, and on the iodine-based polarizing film. , A method of transferring the pressure-sensitive adhesive layer may be used, or the pressure-sensitive adhesive composition may be directly applied onto the iodine-based polarizing film to form a pressure-sensitive adhesive layer.

It does not specifically limit as said base material, For example, various base materials, such as a release film and a transparent resin film base material, are mentioned.

Various methods are used as the coating method to the substrate or the polarizing film. Specifically, for example, fountain coater, roll coating, kiss roll coating, gravure coating, reverse coating, roll brush, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, die Methods, such as an extrusion coating method using a coater or the like, are mentioned.

The drying conditions (temperature, time) are not particularly limited, and may be appropriately set according to the composition and concentration of the pressure-sensitive adhesive composition, but for example, at about 80 to 170°C, preferably 90 to 200°C, for 1 to 60 minutes, preferably It is 2 to 30 minutes.

The thickness (after drying) of the pressure-sensitive adhesive layer is preferably 5 to 100 µm, more preferably 7 to 70 µm, and still more preferably 10 to 50 µm, for example. When the thickness of the pressure-sensitive adhesive layer is less than 7 µm, the adhesion to the adherend becomes insufficient, and thus durability under high temperature and high temperature and humidity tends to be insufficient. On the other hand, when the thickness of the pressure-sensitive adhesive layer exceeds 70 μm, the pressure-sensitive adhesive composition is not sufficiently dried during application and drying when forming the pressure-sensitive adhesive layer, and air bubbles remain, or thickness non-uniformity occurs on the surface of the pressure-sensitive adhesive layer. As a result, there is a tendency for the appearance problem to be easily present.

As a constituent material of the release film, for example, resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabrics, nets, foam sheets, metal foils, and laminates thereof, etc. Although a suitable thin leaf body etc. are mentioned, since a surface smoothness is excellent, a resin film is used suitably.

Examples of the resin film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film. , A polyurethane film, an ethylene-vinyl acetate copolymer film, etc. are mentioned.

The thickness of the release film is usually 5 to 200 µm, preferably about 5 to 100 µm. If necessary, the release film may be subjected to a release and antifouling treatment with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, or the like, or an antistatic treatment such as a coating type, an additive type, and a vapor deposition type. In particular, by appropriately performing a release treatment such as a silicone treatment, a long chain alkyl treatment, or a fluorine treatment on the surface of the release film, the release property from the pressure-sensitive adhesive layer can be further improved.

Although it does not specifically limit as said transparent resin film base material, Various resin films which have transparency are used. The resin film is formed of a single layer of film. For example, as the material, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefins Resin, (meth)acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin, and the like. Among these, polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.

The thickness of the film substrate is preferably 15 to 200㎛.

Moreover, you may have an anchor layer between an iodine-type polarizing film and an adhesive layer. The material for forming the anchor layer is not particularly limited, and examples thereof include various polymers, metal oxide sol, and silica sol. Among these, polymers are particularly preferably used. The use mode of the polymers may be any of a solvent-soluble type, an aqueous dispersion type, and an aqueous solution type.

Examples of the polymers include polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, polyvinylpyrrolidone, and polystyrene resins. Among these, polyurethane resins, polyester resins, and acrylic resins are particularly preferred. A crosslinking agent can be appropriately blended into these resins. One of these other binder components, or two or more of them can be suitably used according to the purpose. The thickness of the anchor layer is not particularly limited, but it is preferably 5 to 300 nm.

The method for forming the anchor layer is not particularly limited, and it can be carried out by a generally known method. In addition, when the anchor layer is formed, the iodine-based polarizing film may be subjected to an activation treatment. Various methods can be employed for the activation treatment, and for example, corona treatment, low pressure UV treatment, plasma treatment, and the like can be employed.

The method of forming the pressure-sensitive adhesive layer on the anchor layer on the iodine-based polarizing film is as described above.

In addition, when the pressure-sensitive adhesive layer of the polarizing film provided with the pressure-sensitive adhesive layer for transparent conductive films of the present invention is exposed, the pressure-sensitive adhesive layer may be protected with a release film (separator) until it is provided for practical use. As a release film, the thing mentioned above is mentioned. When a release film is used as a base material at the time of producing the pressure-sensitive adhesive layer, by bonding the pressure-sensitive adhesive layer on the release film and an iodine-based polarizing film, the release film is a pressure-sensitive adhesive layer release of a polarizing film provided with a pressure-sensitive adhesive layer for a transparent conductive film. It can be used as a film, and simplification in terms of the process is possible.

2. Laminate

In the laminate of the present invention, the polarizing film provided with the pressure-sensitive adhesive layer for a transparent conductive film and the member having a transparent conductive film are transparent of the pressure-sensitive adhesive layer of the polarizing film provided with the pressure-sensitive adhesive layer for the transparent conductive film and the member having the transparent conductive film. It is characterized in that the conductive film is bonded to come into contact.

The polarizing film provided with the pressure-sensitive adhesive layer for a transparent conductive film may be the one described above.

The member having a transparent conductive film is not particularly limited, and a known member can be used. Examples thereof include a member having a transparent conductive film on a transparent substrate such as a transparent film, and a member having a transparent conductive film and a liquid crystal cell.

As the transparent substrate, any one having transparency may be used, and for example, a resin film, a substrate made of glass or the like (for example, a sheet-like, film-like, plate-like substrate, etc.) may be mentioned, and a resin film is particularly preferred. . The thickness of the transparent substrate is not particularly limited, but is preferably about 10 to 200 µm, and more preferably about 15 to 150 µm.

Although it does not specifically limit as a material of the said resin film, Various plastic materials which have transparency are mentioned. For example, as the material, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefins Resin, (meth)acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin, and the like. Among these, polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.

In addition, the transparent substrate is subjected to etching treatment or undercoating treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, etc. on the surface in advance, and adhesion of a transparent conductive film provided thereon to the transparent substrate You may try to improve. In addition, before the transparent conductive film is provided, it may be subjected to vibration suppression and cleaning by solvent cleaning or ultrasonic cleaning, if necessary.

The material constituting the transparent conductive film is not particularly limited, and at least one selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, and tungsten Metal oxides of the metals of are used. The metal oxide may further contain metal atoms shown in the group as necessary. For example, indium oxide (ITO) containing tin oxide, tin oxide containing antimony, and the like are preferably used, and ITO is particularly preferably used. As ITO, it is preferable to contain 80 to 99 weight% of indium oxide and 1 to 20 weight% of tin oxide.

In addition, examples of the ITO include crystalline ITO and amorphous (amorphous) ITO. Crystalline ITO can be obtained by applying a high temperature during sputtering or by further heating amorphous ITO. Since the above deterioration due to iodine occurs remarkably in amorphous ITO, the polarizing film provided with the pressure-sensitive adhesive layer for transparent conductive films of the present invention is particularly effective in amorphous ITO.

The thickness of the transparent conductive film is not particularly limited, but is preferably 7 nm or more, more preferably 12 to 60 nm, and even more preferably 18 to 45 nm. When the thickness of the transparent conductive film is less than 7 nm, deterioration of the transparent conductive film due to iodine tends to occur, and the change in the electric resistance value of the transparent conductive film tends to increase. On the other hand, when it exceeds 60 nm, the productivity of the transparent conductive film decreases, the cost increases, and the optical properties tend to decrease.

The method for forming the transparent conductive film is not particularly limited, and a conventionally known method can be employed. Specifically, a vacuum evaporation method, a sputtering method, and an ion plating method can be illustrated, for example. In addition, an appropriate method may be employed depending on the required film thickness.

The thickness of the substrate having the transparent conductive film is, for example, 15 to 200 μm. Further, from the viewpoint of thinning, it is preferably 15 to 150 µm, and more preferably 15 to 50 µm. When the substrate having the transparent conductive film is used as a resistive film, for example, a thickness of 100 to 200 μm may be used. In addition, when used in the electrostatic capacity method, for example, a thickness of 15 to 100 µm is suitable. In particular, a thickness of 15 to 50 µm is more preferable, and a thickness of 20 to 50 µm is required in response to the recent demand for further thinning. More preferable.

Moreover, an undercoat layer, an oligomer prevention layer, etc. can be provided between a transparent conductive film and a transparent base material as needed.

In addition, as a member having a transparent conductive film and a liquid crystal cell, the liquid crystal cell including the configuration of a substrate (eg, glass substrate, etc.)/liquid crystal layer/substrate used in image display devices such as various liquid crystal displays. An example is given to having a transparent conductive film on the side of the substrate not in contact with the liquid crystal layer. Moreover, when a color filter substrate is provided on a liquid crystal cell, you may have a transparent conductive film on the said color filter. The method of forming the transparent conductive film on the substrate of the liquid crystal cell is the same as described above.

When the polarizing film provided with the pressure-sensitive adhesive layer for transparent conductive films of the present invention is bonded to the transparent conductive film, the change rate of the resistance value of the transparent conductive film is preferably less than 400%, preferably 200% or less, and more preferably 150% or less. And more preferably 120% or less. The rate of change of the resistance value is preferably less than 400% from the standpoint of measures against static unevenness and shielding functions, and is preferably 10 to 20% in the case of a sensor application. The rate of change in the resistance value of the transparent conductive film can be measured by the method described in Examples.

3. Image display device

The laminate of the present invention is an image display device (liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel), electronic paper, etc.) equipped with an input device (touch panel, etc.), input device Although it can be suitably used in the manufacture of a substrate (member) constituting a device such as (touch panel, etc.) or a substrate (member) used in this device, it can be particularly suitably used in the manufacture of optical substrates for touch panels. .

The transparent conductive film obtained by subjecting the laminate of the present invention to a process such as cutting, resist printing, etching, silver ink printing, or the like can be used as a substrate (optical member) for an optical device. The substrate for an optical device is not particularly limited as long as it has optical properties, but, for example, an image display device (a liquid crystal display device, an organic EL (electroluminescence) display device, a plasma display panel (PDP), electronic paper, etc.) , A base material (member) constituting a device such as an input device (touch panel, etc.) or a base material (member) used in this device.

In addition, the polarizing film provided with the pressure-sensitive adhesive layer for a transparent conductive film of the present invention prevents deterioration of the transparent conductive film even when the transparent conductive film is laminated on the pressure-sensitive adhesive layer of the polarizing film provided with the transparent conductive film as described above. It can suppress, and it is possible to suppress an increase in the surface resistance of the transparent conductive film. Therefore, as long as the pressure-sensitive adhesive layer of the polarizing film provided with the pressure-sensitive adhesive layer for a transparent conductive film is in contact with the transparent conductive film, the polarizing film provided with the pressure-sensitive adhesive layer for a transparent conductive film of the present invention can be suitably used. For example, a liquid crystal panel having a polarizing film and a transparent conductive film provided with an adhesive layer for a transparent conductive film of the present invention, so that the adhesive layer of the polarizing film provided with the adhesive layer for a transparent conductive film and the transparent conductive film of the liquid crystal panel contact It can be bonded to form an image display device.

In addition, for the touch panel, a method such as a touch panel such as a resistive film method or a capacitive method, an on-cell touch panel in which an electrode made of a transparent conductive film is formed on a glass substrate on a liquid crystal cell, or a transparent conductive film The electrode can be used regardless of the configuration of an in-cell type touch panel in which the inside of a liquid crystal cell is introduced.

(Example)

Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the following examples unless the gist is exceeded. In addition, in each example, both parts and% are based on weight, and the room temperature standing conditions which are not particularly specified below are all 23°C and 65% R.H.

<Iodine content in polarizer>

The iodine content (content of iodine and/or iodine ion) in the polarizer was measured according to the following procedure.

1) Fluorescent X-ray intensity was measured for a plurality of polarizers containing a predetermined amount of potassium iodide, and a relational expression between iodine content and fluorescent X-ray intensity was derived.

2) Fluorescent X-rays of an iodine polarizer having an unknown iodine content were measured, and the amount of iodine was calculated from the numerical value using the above relational formula.

<Measurement of moisture permeability of transparent protective film>

It measured according to the moisture permeability test (cup method) of JISZO208. The transparent protective film cut into a diameter of 60 mm was set in a moisture-permeable cup containing about 15 g of calcium chloride, placed in a thermostat at 60° C. and 90% RH, and left to stand for 24 hours, and then the weight increase of calcium chloride was measured to measure the moisture permeability (g/( m ² ·24h)) was obtained.

<Measurement of weight average molecular weight (Mw) of acrylic polymer>

The weight average molecular weight of the produced acrylic polymer was measured by GPC (gel transmission chromatography).

Device: HLC-8220GPC, manufactured by Tosoh Corporation

column:

Sample column; Tosoh Corporation, TSKguardcolumn Super HZ-H (1EA) + TSKgel Super HZM-H (2EA)

Reference column; Tosoh Corporation, TSKgel Super H-RC (1 pc.)

Flow: 0.6 mL/min

Injection volume: 10 μL

Column temperature: 40°C

Eluent: THF

Injection sample concentration: 0.2% by weight

Detector: differential refractometer

In addition, the weight average molecular weight was calculated in terms of polystyrene.

Production Example 1 (Preparation of the polarizing film 1)

A polyvinyl alcohol film having a thickness of 80 µm was stretched three times while dyeing for 1 minute in an iodine solution having a concentration of 30°C and 0.3% between rolls having different speed ratios. Thereafter, the total draw ratio was extended to 6 times while immersed for 0.5 minutes in an aqueous solution containing 60°C, boric acid at a concentration of 4% and potassium iodide at a concentration of 10%. Subsequently, after washing by immersing for 10 seconds in an aqueous solution containing potassium iodide at 30°C and 1.5% concentration, it was dried at 50°C for 4 minutes, and a polarizer (A-1) having a thickness of 25 μm and an iodine content of 2.3% by weight was prepared. Got it. A PVA-based resin aqueous solution was applied to one side of the polarizer (A-1), and an acrylic film having a thickness of 40 µm (moisture permeability: 250 g/(m ² ·24h)) was bonded to prepare a polarizing film (1). The transmittance of the obtained polarizing film 1 was 43%.

Production Example 2 (Preparation of the polarizing film 2)

The polarizer (A-2) having a thickness of 25 µm and an iodine content of 3.1% by weight was carried out in the same manner as in Production Example 1 except that the concentrations and immersion times of the various solutions of Production Example 1 were adjusted so that the transmittance of the polarizing film was 40%. ). A PVA-based resin aqueous solution was applied to one side of the polarizer (A-2), and an acrylic film having a thickness of 40 µm (moisture permeability: 250 g/(m ² ·24h)) was bonded to prepare a polarizing film 2. The transmittance of the obtained polarizing film 2 was 40%.

Manufacturing Example 3 (Preparation of Polarizing Film 3)

Corona treatment was performed on one side of a thermoplastic resin substrate (long-shaped amorphous polyethylene terephthalate film, thickness: 100 μm, water absorption: 0.60 wt%, Tg: 80°C), and on this corona treated side, a degree of polymerization of 4200 and a degree of saponification A 99.2 mol% aqueous solution of polyvinyl alcohol was applied and dried at 60° C. to form a 10 μm-thick PVA-based resin layer to prepare a laminate.

The obtained laminate was uniaxially stretched at the free end 2.0 times in the longitudinal direction (length direction) between rolls having different circumferential speeds in an oven at 120°C (air auxiliary stretching), and then the laminate was insoluble at a liquid temperature of 30°C. It was immersed for 30 seconds in a heating bath (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid based on 100 parts by weight of water) for 30 seconds (insolubilization treatment).

The laminate after the insolubilization treatment was immersed for 60 seconds in a dyeing bath at a liquid temperature of 30°C (an iodine aqueous solution obtained by blending 0.2 parts by weight of iodine and 1.0 parts by weight of potassium iodide) for 60 seconds (dyeing treatment) Then, it was immersed for 30 seconds in a crosslinking bath at a liquid temperature of 30°C (a boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and 3 parts by weight of boric acid) at a liquid temperature of 30°C (crosslinking treatment).

Thereafter, the laminate was immersed in an aqueous solution of boric acid at a liquid temperature of 70°C (an aqueous solution obtained by mixing 4 parts by weight of boric acid and 5 parts by weight of potassium iodide) at a liquid temperature of 70°C. In the direction (longitudinal direction), uniaxial stretching was performed so that the total draw ratio was 5.5 times (underwater stretching), and then, the laminate was mixed in a washing bath at a liquid temperature of 30°C (4 parts by weight of potassium iodide was added to 100 parts by weight of water). The obtained aqueous solution) was immersed (washing treatment).

By the above series of treatments, an optical film layered product including a polarizer (B-1) having a thickness of 5 µm and an iodine content of 8% by weight was obtained on a resin substrate.

Subsequently, a PVA-based resin aqueous solution was applied to one side of the polarizer (B-1) of the obtained optical film laminate, and an acrylic film having a thickness of 40 µm (moisture permeability: 250 g/(m ² ·24 h)) was laminated, and 60 It heated for 5 minutes in an oven maintained at °C, and the thermoplastic resin substrate was peeled off to prepare a polarizing film (3). The transmittance of the obtained polarizing film 3 was 43%.

Production Example 4 (Preparation of Polarizing Film 4)

The polarizer (B-2) having a thickness of 5 μm and an iodine content of 11% by weight was carried out in the same manner as in Production Example 3 except that the concentrations and immersion times of various solutions of Production Example 3 were adjusted so that the transmittance of the polarizing film was 40%. ). On one side of the polarizer (B-2), a PVA-based resin aqueous solution was applied, an acrylic film having a thickness of 40 µm (moisture permeability: 250 g/(m ² ·24h)) was laminated, and in an oven maintained at 60° C. for 5 minutes It heated and peeled off a thermoplastic resin base material, and the polarizing film 4 was produced. The transmittance of the obtained polarizing film 4 was 40%.

Production Example 5 (Preparation of the polarizing film 5)

A polarizer (B-3) having a thickness of 5 µm and an iodine content of 5% by weight was carried out in the same manner as in Production Example 3, except that the concentrations and immersion times of various solutions of Production Example 3 were adjusted so that the transmittance of the polarizing film was 45%. ). On one side of the polarizer (B-3), a PVA-based resin aqueous solution was applied, an acrylic film having a thickness of 40 µm (moisture permeability: 250 g/(m ² ·24h)) was laminated, and in an oven maintained at 60°C for 5 minutes It heated and peeled off a thermoplastic resin base material, and the polarizing film 5 was produced. The transmittance of the obtained polarizing film 5 was 45%.

Production Example 6 (Preparation of Polarizing Film 6)

The transparent protective film of Production Example 3 was obtained from an acrylic film having a thickness of 40 μm (moisture permeability: 250 g/(m ² · 24 h)), and a cycloolefin polymer (COP)-based film having a thickness of 40 μm (moisture permeability: 10 g/(m ² · 24h) Except having changed to), it carried out similarly to Production Example 3, and obtained the polarizing film 6. The transmittance of the obtained polarizing film 6 was 43 %.

Production Example 7 (Preparation of the polarizing film 7)

The transparent protective film of Production Example 3 was obtained by applying a thin layer of an acrylic polymer to a triacetylcellulose film having a thickness of 40 μm in an acrylic film (moisture permeability: 250 g/(m ² ·24h)) having a thickness of 40 μm ( TAC-HC, acrylic coating film thickness: 10 µm, moisture permeability: 700 g/(m ² ·24 h)), except for changing to), was carried out in the same manner as in Production Example 3 to obtain a polarizing film 7. The transmittance of the obtained polarizing film 7 was 43%.

Production Example 8 (Preparation of the polarizing film 8)

A transparent protective film of Preparation Example 3, an acrylic film having a thickness of 40㎛ was changed ^{to:: (470g / (m 2} · 24h) water vapor permeability) (water vapor transmission rate ^{250g / (m 2 · 24h)} ), an acrylic film having a thickness of from 20㎛ Except that, it carried out similarly to manufacture example 3, and obtained the polarizing film (8). The transmittance of the obtained polarizing film 8 was 43%.

Production Example 9 (Preparation of the polarizing film 9)

The transparent protective film of Production Example 4 was obtained from a 40 μm-thick acrylic film (moisture permeability 250 g/(m ² ·24h)) and a 40 μm-thick triacetylcellulose film (moisture permeability: 1200 g/(m ² ·24h)) Except having changed to ), it carried out similarly to manufacture example 4, and obtained the polarizing film (9). The transmittance of the obtained polarizing film 9 was 40%.

Production Example 10 (Preparation of the polarizing film 10)

The polarizer (B-4) having a thickness of 5 µm and an iodine content of 15% by weight was carried out in the same manner as in Production Example 3 except that the concentrations and immersion times of various solutions of Production Example 3 were adjusted so that the transmittance of the polarizing film was 38%. ). On one side of the polarizer (B-4), an acrylic film having a thickness of 40 μm (moisture permeability: 250 g/(m ² ·24h)) was bonded to prepare a polarizing film 10. The transmittance of the obtained polarizing film 10 was 38%.

The polarizing films (1) to (10) obtained in Production Examples 1 to 10 are as follows.

(Example 1)

(Preparation of acrylic pressure-sensitive adhesive composition)

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirring device, 84.95 parts by weight of butyl acrylate, 0.05 parts by weight of acrylic acid, 5 parts by weight of 4-hydroxybutyl acrylate, 10 parts by weight of N-vinyl-2-pyrrolidone As a part and initiator, 0.1 part of AIBN was added with ethyl acetate with respect to 100 parts of the monomer (solid content), reacted for 7 hours at 55° C. under a stream of nitrogen gas, and then ethyl acetate was added to the reaction solution to obtain a weight average molecular weight of 1.6 million. A solution containing an acrylic polymer was obtained (solid content concentration 30% by weight). As a crosslinking agent, per 100 parts of the solid content of the acrylic polymer solution, 0.2 parts by weight of dibenzoyl peroxide (trade name: Niper BMT, manufactured by Nippon Yushi Co., Ltd.) as a peroxide, trimethylolpropane xylene diisocyanate (trade name: Takenate) as an isocyanate crosslinking agent 0.1 parts of D110N, manufactured by Mitsui Chemicals Co., Ltd. and 0.08 parts of a silane coupling agent (trade name: KBM403, manufactured by Shin-Etsu Chemical Industries, Ltd.) were blended to obtain an acrylic pressure-sensitive adhesive composition (1).

(Preparation of a polarizing film with an adhesive layer)

The acrylic pressure-sensitive adhesive composition (1) was uniformly applied to the surface of a polyethylene terephthalate film (substrate) treated with a silicone-based release agent with a fountain coater, dried in an air circulation constant temperature oven at 155°C for 2 minutes, and A pressure-sensitive adhesive layer having a thickness of 20 μm was formed on the surface. Subsequently, the separator in which the pressure-sensitive adhesive layer was formed was attached to the surface (polarizer surface) of the polarizing film 1 obtained in Production Example 1 without a transparent protective film, thereby producing a polarizing film with a pressure-sensitive adhesive layer. The moisture content of the obtained pressure-sensitive adhesive layer was 1.3% by weight.

(Example 2)

(Preparation of acrylic pressure-sensitive adhesive composition)

In a reaction vessel equipped with a cooling tube, a nitrogen inlet tube, a thermometer and a stirring device, 99 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, and 0.1 part of AIBN as an initiator per 100 parts of the monomer (solid content) with ethyl acetate and After they were added together and reacted at 60° C. for 7 hours in a nitrogen gas stream, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer with a weight average molecular weight of 1.6 million (solid content concentration 30% by weight). As a crosslinking agent, per 100 parts of the solid content of the acrylic polymer solution, 0.1 parts of trimethylolpropane xylene diisocyanate (trade name: Takenate D110N, manufactured by Mitsui Chemical Co., Ltd.), 0.3 parts of dibenzoyl peroxide, and γ as a silane coupling agent -Glycidoxypropyltrimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 0.075 parts, and as a phenolic antioxidant, pentaerythritol tetrakis[3-(3,5-di-) 0.3 parts of tert-butyl-4-hydroxyphenyl) propionate (IRGANAOX 1010, manufactured by BASF Japan Co., Ltd.) was blended to obtain an acrylic pressure-sensitive adhesive composition (2).

(Preparation of a polarizing film with an adhesive layer)

In Example 1 (Preparation of a polarizing film with an adhesive layer), except for changing the acrylic pressure-sensitive adhesive composition (1) to the acrylic pressure-sensitive adhesive composition (2), in the same manner as in Example 1, the pressure-sensitive adhesive layer is provided The prepared polarizing film was produced. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Example 3)

(Preparation of acrylic pressure-sensitive adhesive composition)

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirring device, 99.9 parts of 2-ethylhexyl acrylic acid, 0.1 parts of 6-hydroxyhexyl acrylic acid, and 0.1 part of AIBN as an initiator per 100 parts of the monomer (solid content) After addition with ethyl acetate and reacting at 60°C for 7 hours under a stream of nitrogen gas, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer having a weight average molecular weight of 1.8 million (solid content concentration 30% by weight). As a crosslinking agent, per 100 parts of the solid content of the acrylic polymer solution, an adduct body of trimethylolpropane/tolylene diisocyanate (trade name: Coronate L, manufactured by Nippon Polyurethane Industrial Co., Ltd.) is 0.1 parts and dioctyl tin dilaurate. -Based crosslinking accelerator (trade name: Enviizer OL-1, manufactured by Tokyo Fine Chemical Co., Ltd.) 0.03 parts, γ-glycidoxypropyltrimethoxysilane (trade name: KBM-403, Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent ) Agent) was blended to obtain an acrylic pressure-sensitive adhesive composition (3).

(Preparation of a polarizing film with an adhesive layer)

In the (Preparation of a polarizing film with an adhesive layer) of Example 1, except for changing the acrylic pressure-sensitive adhesive composition (1) to the acrylic pressure-sensitive adhesive composition (3), in the same manner as in Example 1, the pressure-sensitive adhesive layer is provided. The prepared polarizing film was produced. The moisture content of the obtained pressure-sensitive adhesive layer was 0.3% by weight.

(Examples 4 to 7)

Except having changed the polarizing film (1) to the polarizing films (2) to (5) obtained in Production Examples 2 to 5 in (Preparation of a polarizing film with an adhesive layer) of Example 1, Example 1 In the same manner as, a polarizing film provided with an adhesive layer was produced. The moisture content of the obtained pressure-sensitive adhesive layer was 1.3% by weight.

(Example 8)

(Preparation of acrylic pressure-sensitive adhesive composition)

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirring device, 84.95 parts by weight of butyl acrylate, 0.05 parts by weight of acrylic acid, 5 parts by weight of hydroxyethyl acrylate, 10 parts by weight of N-vinyl-2-pyrrolidone, and 0.1 part of AIBN as an initiator was added with ethyl acetate with respect to 100 parts of the monomer (solid content), reacted at 55° C. for 7 hours under a stream of nitrogen gas, and then ethyl acetate was added to the reaction solution to obtain an acrylic polymer with a weight average molecular weight of 1.6 million. A containing solution was obtained (solid content concentration 30% by weight). Per 100 parts of the solid content of the acrylic polymer solution as a crosslinking agent, 0.2 parts by weight of dibenzoyl peroxide (brand name: Niper BMT, manufactured by Nippon Yushi Co., Ltd.) as a peroxide, trimethylolpropane xylene diisocyanate (brand name: Takenate D110N) as an isocyanate crosslinking agent , Mitsui Chemical Co., Ltd. product) was mixed with 0.1 part and a silane coupling agent (trade name: KBM403, Shin-Etsu Chemical Co., Ltd. product) 0.08 part was blended, and the acrylic adhesive composition (4) was obtained.

(Preparation of a polarizing film with an adhesive layer)

In (Preparation of a polarizing film with an adhesive layer) of Example 1, the acrylic pressure-sensitive adhesive composition (1) was changed to an acrylic pressure-sensitive adhesive composition (4), and the polarizing film (1) was obtained from the polarizing film ( Except having changed to 3), it carried out similarly to Example 1, and produced the polarizing film provided with the adhesive layer. The moisture content of the obtained pressure-sensitive adhesive layer was 1.3% by weight.

(Example 9)

Except having changed the polarizing film 1 to the polarizing film 3 obtained in Production Example 3 in (Preparation of a polarizing film with an adhesive layer) of Example 2, it carried out similarly to Example 2, and the adhesive layer This provided polarizing film was produced. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Example 10)

Except having changed the polarizing film 1 to the polarizing film 3 obtained in Production Example 3 in (Preparation of a polarizing film with an adhesive layer) of Example 3, it carried out similarly to Example 3, and the adhesive layer This provided polarizing film was produced. The moisture content of the obtained pressure-sensitive adhesive layer was 0.3% by weight.

(Example 11)

Except having changed the polarizing film 1 to the polarizing film 4 obtained in Production Example 4 in (Preparation of the polarizing film with an adhesive layer) of Example 2, it carried out similarly to Example 2, and the adhesive layer This provided polarizing film was produced. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Examples 12 to 14)

In Example 1 (Preparation of a polarizing film with an adhesive layer), Example 1 except that the polarizing film 1 was changed to the polarizing films 6 to (8) obtained in Production Examples 6 to 8 In the same manner as, a polarizing film provided with an adhesive layer was produced. The moisture content of the obtained pressure-sensitive adhesive layer was 1.3% by weight.

(Example 15)

(Preparation of monomer components used in UV polymerization)

2-ethylhexyl acrylate 61 parts by weight, N-vinyl-2-pyrrolidone 14 parts by weight, two kinds of photoinitiators (trade name: Irgacure 184, manufactured by BASF) 0.05 parts by weight and photoinitiators (trade name: Irga Cure 651 (manufactured by BASF) 0.05 parts by weight were added to a four neck flask to prepare a monomer mixture. Subsequently, the monomer mixture was exposed to ultraviolet rays in a nitrogen atmosphere and partially photopolymerized to obtain a partial polymer (acrylic polymer syrup) having a polymerization rate of about 10% by weight.

To the total amount of the acrylic polymer syrup obtained (75.1 parts by weight), 2-hydroxyethyl acrylate (2HEA) 3 parts by weight, 4-hydroxybutyl acrylate (HBA) 22 parts by weight, dipentaerythritol pentaacrylate (brand name : After adding 0.12 parts by weight of KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., these were uniformly mixed to prepare a monomer component.

(Preparation of adhesive layer by UV polymerization)

Subsequently, the monomer component adjusted above was peeled off on one side with silicone on the peeling-treated side of a 38 μm-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi City Corporation), and the final thickness was 20 The coating layer was formed by coating so as to be µm. Subsequently, on the surface of the applied monomer component, a 38 μm-thick polyester film (trade name: Diafoil MRE, manufactured by Mitsubishi City Corporation) was peeled off with silicone on one side, and the peeling-treated side of the film was on the side of the coating layer. It was covered as possible. Thereby, the coating layer of the monomer component was blocked from oxygen. Using a chemical light lamp (manufactured by Toshiba Co., Ltd.) to the sheet having the coating layer thus obtained, ultraviolet rays of an illuminance of 5 mW/cm ² (measured by Topcon UVR-T1 with maximum sensitivity at about 350 nm) were irradiated for 360 seconds. Then, the coating layer was cured to form an adhesive layer, and an adhesive sheet was prepared. The polyester film coated on both sides of the pressure-sensitive adhesive layer functions as a release liner (separator).

(Preparation of a polarizing film with an adhesive layer)

Polarization with a pressure-sensitive adhesive layer by peeling the separator of the pressure-sensitive adhesive layer on only one side, and attaching the separator with the pressure-sensitive adhesive layer to the side without a transparent protective film (polarizer surface) of the polarizing film 3 obtained in Preparation Example 3 The film was produced. The moisture content of the obtained pressure-sensitive adhesive layer was 3.1% by weight.

(Comparative Example 1)

Except having changed the polarizing film 1 to the polarizing film 9 obtained in Production Example 9 in (Preparation of a polarizing film with an adhesive layer) of Example 1, it carried out similarly to Example 1, and the adhesive layer This provided polarizing film was produced. The moisture content of the obtained pressure-sensitive adhesive layer was 1.3% by weight.

(Comparative Example 2)

(Preparation of emulsion type acrylic pressure-sensitive adhesive composition)

To the container, 780 parts of butyl acrylate, 200 parts of methyl methacrylate, and 20 parts of acrylic acid were added and mixed to obtain a monomer mixture. Subsequently, 30 parts of Aqualon HS-10 (manufactured by Daiichi Industries Pharmaceutical Co., Ltd.) and 635 parts of ion-exchanged water were added to 1000 parts of the monomer mixture prepared in the above ratio, and a homomixer (Tokushu Gika It stirred at 6000 (rpm) for 5 minutes using the Kyoko Co., Ltd. product, and the monomer emulsion was prepared.

Next, 200 parts of the monomer emulsion prepared above and 515.9 parts of ion-exchanged water were added to a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, a dropping funnel, and a stirring blade, and then, the reaction vessel was sufficiently replaced with nitrogen. After that, 0.6 parts of ammonium persulfate was added, followed by polymerization at 60°C for 1 hour while stirring. Subsequently, the remaining monomer emulsion was added dropwise thereto over 3 hours while maintaining the reaction vessel at 60°C, and then polymerized for 3 hours to obtain a polymer emulsion having a solid content concentration of 46.2%. Subsequently, after cooling the polymer emulsion to room temperature, 10% aqueous ammonia was added thereto to set the pH to 8, and an emulsion-type acrylic pressure-sensitive adhesive adjusted to 45.6% solid content was obtained.

(Preparation of a polarizing film with an adhesive layer)

After applying the emulsion-type acrylic pressure-sensitive adhesive to a release film (brand name: Diafoil MRF-38, polyethylene terephthalate base material, manufactured by Mitsubishi Chemical Polyester Co., Ltd.) so that the thickness after drying becomes 20 μm, by a die coater , Dried at 120° C. for 5 minutes to form a pressure-sensitive adhesive layer. Subsequently, the separator in which the pressure-sensitive adhesive layer was formed was attached to the surface (polarizer surface) of the polarizing film 4 obtained in Production Example 4 without a transparent protective film to prepare a polarizing film with a pressure-sensitive adhesive layer. The moisture content of the obtained pressure-sensitive adhesive layer was 5.0% by weight.

(Preparation of a polarizing film with an adhesive layer)

In (Preparation of a polarizing film with an adhesive layer) of Example 1, the acrylic pressure-sensitive adhesive composition (1) was changed to an acrylic pressure-sensitive adhesive composition (5), and the polarizing film (1) was obtained from the polarizing film ( Except having changed to 4), it carried out similarly to Example 1, and produced the polarizing film provided with the adhesive layer. The moisture content of the obtained pressure-sensitive adhesive layer was 3.2% by weight.

(Comparative Example 3)

Except having changed the polarizing film 1 to the polarizing film 10 obtained in Production Example 10 in (Preparation of the polarizing film with an adhesive layer) of Example 1, it carried out similarly to Example 1, and the adhesive layer This provided polarizing film was produced. The moisture content of the obtained pressure-sensitive adhesive layer was 1.3% by weight.

About the polarizing film provided with the adhesive layer obtained by the Example and the comparative example, the following ITO glass deterioration test was performed. The results are shown in Table 2.

<Measurement method of saturated moisture content of the adhesive layer>

Samples of about 50 mg were taken from the pressure-sensitive adhesive layer of the polarizing film provided with the pressure-sensitive adhesive layer prepared in Examples and Comparative Examples. The sample was measured for weight (W1) in a state where moisture was completely removed under conditions of 1 hour at 100°C using a moisture adsorption/desorption measuring device (IGA-Sorp, manufactured by Hiden), and then 23°C 0% RH At 2 hours, 23°C, 55% RH for 5 hours, 60°C, 90% RH for 5 hours, 23°C and 55% RH for 5 hours, and the weight change was observed. When the weight change of the sample disappeared (saturated state), the weight (W2) was measured. The saturated moisture content was measured from the following equation.

<ITO glass degradation test>

(Preparation of an adherend having a crystalline ITO layer and amorphous ITO)

An ITO film was formed on one side of an alkali-free glass by sputtering, and an adherend having a crystallized ITO thin film and an adherend having an amorphous ITO film were produced. Each to-be-adhered body was subjected to a heat treatment at 140° C. for 30 minutes before bonding with the polarizing film provided with the pressure-sensitive adhesive layer. The Sn ratio of the crystalline ITO thin film was 10% by weight. The Sn ratio of the amorphous ITO thin film was 3% by weight. In addition, the method of calculating the Sn ratio of the ITO thin film is as described above.

(Measurement of change rate of resistance value)

The adherend having the ITO thin film was cut into 25 mm × 25 mm, and the polarizing film provided with the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was cut into 15 mm × 15 mm in the center of the ITO thin film, and the pressure-sensitive adhesive layer and the ITO thin film After bonding so that this contact may be made, what was autoclaved at 50°C for 15 minutes at 5 atm was used as a corrosion resistance measurement sample. The obtained sample for measurement was measured using a measuring device described later, and this was taken as an "initial resistance value". Thereafter, the measurement sample was put into an environment at a temperature of 60°C and 90% R.H. for 500 hours, and then the measurement was taken as "resistance value after moist heat". In addition, the said resistance value was measured using HL5500PC manufactured by Accent Optical Technologies. From the "initial resistance value" and "resistance value after moist heat" measured as described above, the resistance value change rate was calculated by the following equation, and evaluated according to the following evaluation criteria.

1: resistance change rate is less than 120%

2: Resistance change rate exceeds 120% and less than 150%

3: The resistance change rate exceeds 150% and is less than 200%

4: Resistance change rate exceeds 200% and less than 300%

5: Resistance change rate exceeds 300% and less than 400%

6: resistance change rate of 400% or more

In addition, the types of ITO used for measurement are shown in Table 2.

<Durability test>

The separator film of the polarizing film sample provided with the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was peeled off, bonded to the ITO surface of a glass on which amorphous ITO was formed, and subjected to an autoclave treatment at 50° C., 5 atm for 15 minutes, and then 80 It was put into a heating oven at °C and a thermo-hygrostat of 60 °C/90% RH. Peeling and foaming of the polarizing film after 500 hours were observed visually, and evaluated according to the following evaluation criteria.

○: Completely peeling or foaming was not observed.

?: Small peeling or foaming that cannot be confirmed with the naked eye was observed.

×: Clear peeling or foaming was observed.

The iodine content in Table 2 is the content (% by weight) of iodine and/or iodine ion in the polarizer.

Claims (9)

It is a polarizing film provided with an adhesive layer in which an adhesive layer is laminated on at least one side of an iodine-based polarizing film,
The iodine-based polarizing film is a single-sided protective polarizing film having a transparent protective film only on one side of the iodine-based polarizing film, and the side of the one-sided protective polarizing film which does not have a transparent protective film and the pressure-sensitive adhesive layer are in contact,
The iodine-based polarizing film contains 1 to 14% by weight of iodine and/or iodine ions, and on one side of an iodine polarizer having a thickness of 2 to 40 μm, the moisture permeability at 60° C. and 90% RH is 1000 g/(m). ^It is an iodine-based polarizing film having a transparent protective film of ² 24 h) or less,
The pressure-sensitive adhesive layer contains, as a base polymer, an acrylic polymer obtained by solution polymerization, and the saturated moisture content at 60°C and 90% RH is 3.5% by weight or less,
A polarizing film provided with a pressure-sensitive adhesive layer for a transparent conductive film, characterized in that it is used so that the pressure-sensitive adhesive layer and a transparent conductive film of a transparent conductive member having a transparent conductive film contact each other. The polarizing film with a pressure-sensitive adhesive layer for a transparent conductive film according to claim 1, wherein a value obtained by multiplying a polarizer thickness (µm) of the iodine-based polarizer and an iodine content (wt%) is 10 to 80 wt%·µm. . delete The polarizing film according to claim 1, wherein the transparent conductive film is formed of indium tin oxide. The polarizing film with a pressure-sensitive adhesive layer for a transparent conductive film according to claim 4, wherein the indium tin oxide is amorphous indium tin oxide. The polarizing film provided with the pressure-sensitive adhesive layer for a transparent conductive film according to any one of claims 1, 2, 4, and 5, and a transparent conductive member having a transparent conductive film, wherein the pressure-sensitive adhesive layer for a transparent conductive film is provided. A laminate, characterized in that the adhesive layer of the polarizing film and the transparent conductive film of the member are bonded to contact each other. An image display device comprising the laminate according to claim 6. The image display device according to claim 7, wherein the transparent conductive member having the transparent conductive film is a member including a transparent conductive film and a liquid crystal cell. The image display device according to claim 7, wherein the transparent conductive member having a transparent conductive film is a transparent conductive film having a transparent conductive film, and the laminate is used as a touch panel.